Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
  • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
  • B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/10—Formation of a green body
  • B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
  • B22F3/10—Sintering only
  • B22F2003/1042—Sintering only with support for articles to be sintered
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/25—Process efficiency

Definitions

• This invention relates to metal and ceramic containing parts that are formed from powder, and more particularly to a method of making and control of the dimensions of such parts.
• Standard practice in powder metallurgy falls into two basic categories.
• powder pressing powder is placed between two hardened steel dies and compacted, typically to densities of 80% or more. This compaction involves the deforming the powder particles so that they mechanically interlock, thus creating a porous skeleton. Often this skeleton is subsequently infiltrated with a lower melting point material in order to form a fully dense part.
• skeletons of steel powder are often infiltrated with copper alloys.
• the techniques of metal injection molding are used, where a powder is mixed with a binder material and is injected into a die. After the binder has solidified, the powder component is removed. This green part is typically approximately 60% dense. The binder is then burned off or removed chemically and the skeleton is then sintered. Generally speaking, the skeleton is sintered to near full density.
• the two most common approaches for densifying a powder skeleton are either to sinter it to full density or to fill the voids in the skeleton with a second material .
• These voids may be filled by infiltration of a lower melting point metal, or by infiltration of a polymeric material such as an epoxy.
• the skeleton that is formed in the first step of the process may range in density from 55-85%. If sintering to full density is chosen, a significant amount of additional shrinkage must be incurred. The shrinkage arises because material migrates from within the bodies of particles to form larger necks between particles. For example, if a skeleton of 60% density is sintered to full density, the shrinkage must be approximately 18% linear. This large amount of shrinkage can cause significant problems if the goal is to maintain good dimensional accuracy. For example, if a 1% variation in shrinkage is encountered then a dimension which requires a 15% shrink will have an uncertainty of .15% of original. Thus, a 10cm dimension will be uncertain by .15mm, a very significant error when precision components are considered. For this reason, the method of creating a skeleton and then sintering the skeleton to full density in a secondary operation is not attractive when precision parts are concerned.
• 3D Printing A processing technique that uses powders has become known as "three-dimensional printing" (“3D Printing") and is described in general in numerous patents, including: U.S. Patent No. 5,204,055, entitled THREE-DIMENSIONAL PRINTING TECHNIQUES, by Sachs, Haggerty, Cima, and Williams; U.S. Patent No. 5,340,656, entitled THREE-DIMENSIONAL PRINTING TECHNIQUES, by Sachs, Haggerty, Cima, and Williams; U.S. Patent No.
• 3D Printing is also disclosed and discussed in co- pending, co-assigned applications, including: U.S.S.N.
• the flexibility of the 3D Printing process makes it possible to construct a part out of any material available in powdered form. Such a part can possess almost any geometry, including overhangs, undercuts, and internal volumes.
• the 3D Printing process was initially developed for the production of ceramic shells and is also useful in making metal parts.
• One key use for such a system is the production of injection molding tooling for plastic parts. Injection molds are used to make a vast array of items, ranging from toys to floppy disks.
• the lead times for the production of such tools generally range from a few weeks to several months.
• the rapid production available via the 3D Printing process can greatly reduce this lead time, thereby alleviating a bottleneck and reducing the duration of product development.
• Such a more severe sintering step is provided to achieve certain mechanical properties, such as higher impact toughness, yield and tensile strengths. It is believed that these properties improve due to increased necking between particles. However, it is just this necking during sintering that causes shrinkage.
• the known 3D Printing process can compensate for a given amount of predicted shrinkage by beginning with a larger green part.
• the shrinkage that occurs during postprocessing is accounted for when the green part is printed.
• the shrinkage has a certain amount ( £ 0.2%) of error associated with it and furthermore is not uniform. This can lead to warped parts whose final dimensions bear some uncertainty. For this reason, alternate powder/binder systems for metal parts are desired.
• the tolerance could be as low as +/-.002 inches (.005 cm) .
• sintering step which draws major bodies of the powder granules together toward each other.
• a goal of the present invention is to minimize or eliminate sintering of the powder granules, and to the extent that any sintering arises, to minimize any shrinkage associated therewith. Because sintering would be reduced or eliminated according to such a possible approach, if densification is desired, it would be necessary to bring the part to full density by some other means, such as infiltration.
• the chosen method of reducing shrinkage and distortion must also provide sufficient part strength and edge definition, and still permit successful infiltration of an infiltrant, if densification is desired. Furthermore, the chosen method must not adversely affect the mechanical properties of the finished part, such as yield and tensile strengths, impact toughness, etc. In fact, it would be preferred that the method of forming the skeleton positively aid in attaining desirable mechanical properties .
• Settering requires an extra step of removing the unprinted regions of the original powder bed; packing the fragile green part in another powder bed, and insuring that all of the fragile regions of the part are supported; and again removing powder from the part after the sintering step. Further, there is an inherent conflict in sintering a part that is settered. The sintering part tends to shrink. However, the supporting settering powder tends to resist any such shrinkage. Moreover, settering is only an adjunct to a sintering step, which has its own drawbacks, as already mentioned.
• an objective of the present invention is to provide a method for fabricating a skeleton with little or no average shrinkage required for its formation and with a higher degree of certainty as to the variation in the shrinkage. It is a further objective of the invention to provide a skeleton that is highly resistant to distortion during subsequent densification steps.
• Another objective of the invention is to provide a liquid binder at specific locations in a powder body, allowing the particles to come to rest substantially in the same positions that they will occupy in the final body, without requiring significant relative motion of the powder particles, and also obtaining a homogeneous combination of powder and liquid, with a high packing fraction.
• Still another object of the invention is to be able to retain fine features, as printed, by safely supporting these printed features through all processing steps.
• Yet another object of the invention is to avoid sintering the main constitutive powder granules throughout the body of the part, with its inherent conflict between the shrinkage of the sintering part and the resistance to shrinkage of any support medium.
• the current invention creates the powder geometry in two distinct steps. In a first step, a powder is placed so that the particles are in maximum contact with each other. Further, the body of powder is shaped as desired, for instance in a layer, or in or around a mold.
• a further material is added in a liquid carrier.
• the further material will provide for the bonding between powder particles.
• the material that joins the powder particles is provided as an independent material. It is a special aspect of the current invention that two different materials are required. One as the main body material and the second as the source for the binding material. Further, there is no movement of the powder particles after they have been placed, i.e., there is no mechanical mixing.
• a preferred implementation is to provide a layer of powder and then to provide the further material within that layer and to repeat this process layer after layer according to a three dimensional printing method, such as is described in U.S. Patent Number 5,204,055, mentioned above.
• the liquid carrier is provided to powder packed in or around a mold.
• a solution of metal salt for instance, an aqueous solution
• the salt solution accumulates at necks between the granules, due to the operation of surface tension.
• a constituent that originates from the salt solution forms at the necks and mechanically joins the granules together.
• the constituent may be crystallized salt itself, or it may be a metal that results from reduction of the salt or some species in between the transformation of salt into metal.
• silver nitrate (AgN0 3 ) solution printed onto stainless steel powder precipitates at necks between granules as the solution dries.
• Another suitable salt is a Rochelle salt C 4 H 4 KNa0 6 -4H 2 0 (sodium potassium tartrate) .
• the precipitated crystallized salt alone is strong enough to maintain the shape of the part as it is subsequently infiltrated.
• the crystallized salt is subsequently reduced by heating it in a suitable environment, which reduction causes the metal (e.g. silver) to deposit onto the powder.
• the conditions of reduction can be chosen so that the metal deposits onto the powder in a thin film.
• some salts require the presence of hydrogen or some other reducing gas in the environment.
• some salts require only that they be heated up and the compound itself disassociates into a metal and other byproducts.
• silver nitrate melts at 212°C forming a yellowish liquid. At 440°C it decomposes into silver, nitrogen, oxygen and nitrogen oxides.
• the salt and a metal powder can be chosen such that upon contact with the metal powder, the salt in the solution reduces to metal, in the solution.
• a principal example of this embodiment of the method of the invention is where the salt and a portion of the metal powder undergo an electrochemical "displacement" reaction. As a result of this reaction the metal of the salt (or a portion of it) is deposited onto the metal powder.
• This deposition of the metal from ionic solutions consists of adding electrons to the dissolved metal ions (of the salt) . These electrons are provided by the metal powder as it partially dissolves into the salt solution.
• silver is the metal of the salt, e.g., silver nitrate
• copper is the metal of the powder.
• Another example is silver carbonate dissolved in ammoniated water undergoing a displacement reaction against molybdenum powder.
• the body after reduction of the metal, is not strong enough for its intended purpose, or for subsequent treatment.
• This approach is possible when the powder in which the salt has been printed has a high enough sintering temperature, T ⁇ , so that it will not begin to sinter or melt during the subsequent heat treatment .
• the powder into which the salt solution has been printed does not have a high enough sintering temperature
• the powder may be held together tightly enough by either the salt crystals, or reduced metal so that it can be removed from the original powder, settered in another, higher temperature powder, and then fired to either reduce the salt to metal, if reduction has not yet taken place, or to sinter or melt the metal from the salt to provide additional strength.
• the crystallized salt form is not strong enough to remove from the surrounding powder but it is desired to remove the body from the powder at that crystallized stage.
• a preferred embodiment of the invention is a method for forming a body from powder using a three- dimensional printing process.
• the method includes the steps of: providing a layer of powder of a first material, granules of the powder layer contacting one another and printing on the layer of powder, a liquid vehicle that contains a salt that will cause the powder granules to be bound together.
• the steps of providing a layer of powder and printing a liquid on the layer are repeated additional times until a desired amount of printed powder has been provided.
• the printed liquid and powder are maintained under conditions such that a further material, which is different from the first material, and which originates from the salt solution, forms at interfaces between the powder granules, and binds adjacent granules to each other within each layer and between layers.
• the further material may be crystallized salt, or reduced metal.
• the maintaining step typically includes drying, and heat treating. The drying can occur in between successive steps of powder deposition, or after all or a larger part of the body to be formed has been formed.
• necks of the further material arise at the points of contact between the granules .
• the subsequent processing may included heat treating these necks to form metal films, or strong metal bodies .
• the powder used is a metal powder
• the liquid vehicle contains a salt that is related to the metal of the powder such that upon contact, metal is deposited onto the powder, even while the liquid is present. This is typically by what is known as a displacement reaction.
• Still another preferred embodiment of the invention is a method for forming a body from powder, comprising the steps of: providing a volume of powder of a first material, granules of the powder volume contacting one another. While maintaining the granules of the volume of powder substantially stationary relative to each other, a liquid vehicle that contains a salt, which will cause the granules to be bound together is provided in the volume of powder. The liquid and powder are maintained under conditions such that a further material, which is different from the first material and which originates from the salt solution, forms at interfaces between the powder granules, and binds adjacent granules to each other.
• This embodiment is not limited to a layered method, and can be used for molding.
• the further material can be crystallized salt, reduced metal, and the metal can be reduced according to a displacement reaction.
• Further processing can include removing the formed part from the original bed when bound by either crystallized salt, reduced metal or a binder, all of which arise at necks between the particles. Further processing can include elevated temperature treatment to sinter or melt the deposited salt or metal, along with settering, if necessary.
• the invention is a method for forming a body from powder with virtually no shrinkage during processing, comprising the steps of: providing a volume of powder of a first material, granules of the powder volume contacting one another; providing in the volume of powder, a liquid vehicle that contains a salt, which will cause the granules to be bound together; and maintaining the liquid and powder under conditions such that a further material, which is different from the first material and which originates from the salt solution, forms at interfaces between the powder granules, and binds adjacent granules to each other, and strengthens the body while shrinking no more than .5% linear.
• the invention is a Solid Freeform Fabrication process, where powder and salt, are co-provided, which salt causes the powder particles to be bound together.
• Yet another preferred embodiment of the invention is a method for forming a body from powder, comprising the steps of providing a volume of powder of a first material, granules of the powder volume contacting one another. A quantity of a salt is provided in the volume of powder, which salt will cause the granules to be bound together. The salt and powder are maintained under conditions such that a further material, which originates from the salt, adheres to said powder granules at interfaces between the powder granules.
• Still another preferred embodiment of the invention is a laser method for forming a body from powder, comprising the steps of: providing a volume of powder of a first material, granules of the powder volume contacting one another. In the volume of powder, a quantity of a salt, is provided, which salt will cause the granules to be bound together. Laser energy is applied to the salt and powder under conditions such that a further material, which originates from the salt, adheres to the powder granules at interfaces between the powder granules.
• Another preferred embodiment of the invention is a fused deposition method for forming a body from powder, comprising the steps of: providing a volume of powder of a first material, granules of the powder volume contacting one another; and providing a binder material, that includes in it a dissolved salt, which salt will cause the granules to be bound together.
• the salt containing binder material is mixed with the volume of powder, and then extruded under conditions such that a further material, which originates from the salt, adheres to said powder granules at interfaces between the powder granules .
• Fig. 1A is a schematic representation of a prior art method of joining loose powder together by sintering
• Fig. IB is a schematic representation of a generic method of the invention, joining loose powder together by a constituent that originates from a salt solution;
• Figs. 2A - 2F is a schematic representation of steps of an embodiment of the invention where a layer of powder is provided (Fig. 2A) a salt solution is printed on a layer of powder (Fig. 2B) , dried (Fig. 2C) , another layer of powder is applied (Fig. 2D) , additional salt solution is printed (Fig. 2E) , and the salt solution is dried to crystals, joining powder granules within and between layers (Fig. 2F) ;
• Fig. 2G is a schematic representation of a step of a reduction embodiment of the invention where the dried salt crystals shown in Fig. 2F are reduced to metal, after heat treatment;
• Fig. 3 is a schematic representation, in flow chart form, of a recrystallization embodiment of the method of the invention.
• Fig. 4 is an electron micrograph of a cross-section of a rochelle salt bound product with a skeleton of stainless steel powder
• Fig. 5A is a schematic representation, in flow chart form, of a reduction embodiment of the method of the invention, where all of the heating of the body is conducted in the original powder bed;
• Fig. 5B is a schematic representation, in flow chart form, of another reduction embodiment of the method of the invention, where the body is removed from the original powder bed and settered after the salt has crystallized, and where all of the heating of the body is conducted in the settering bed;
• Fig. 5C is a schematic representation, in flow chart form, of yet another reduction embodiment of the method of the invention, where the body is removed from the original powder bed and settered after the salt has reduced, and where additional heating of the body to sinter or melt is conducted in the settering bed;
• Fig. 5D is a schematic representation, in flow chart form, of another reduction embodiment of the method of the invention, where a fugitive binder is provided in addition to the salt binder and the body is removed from the original powder bed and settered;
• Fig. 6 is an electron micrograph of a cross-section of a silver nitrate salt bound product with a skeleton of steel powder;
• Fig. 7 is an electron micrograph of a cross-section of a silver nitrate bound product with a skeleton of steel powder, after residing in a forming gas, showing reduction of silver into thin films joining the powder granules;
• Figs . 8A - 81 is a schematic representation of steps of a displacement reaction embodiment of the invention where a layer of powder is provided (Fig. 8A) , a salt solution is printed on a layer of powder (Fig. 8B) , metal is reduced onto the powder by displacement reaction (Fig. 8C) , joining powder granules within the layer, the solution is dried (Fig. 8D) , another layer of powder is applied (Fig. 8E) , additional salt solution is printed (Fig. 8F) , additional metal is reduced onto the powder by displacement reaction, joining powder granules within and between layers (Fig. 8G) , the second deposit of salt solution is dried (Fig. 8H) further joining the powder granules together within and between layers, followed by an optional heat treating step (Fig. 81) which results in the reduction of more metal from salt;
• Fig. 9A is a schematic representation, in flow chart form, of an electrochemical displacement reaction embodiment of the method of the invention.
• Fig. 9B is a schematic representation, in flow chart form, of another electrochemical displacement reaction embodiment of the method of the invention, where the body is further heat treated in the original powder bed to sinter or melt the reduced metal;
• Fig. 9C is a schematic representation, in flow chart form, of still another electrochemical displacement reaction embodiment of the method of the invention, where the body is removed from the original powder bed and settered in another powder, and then further heat treated in the settering bed to sinter or melt the reduced metal;
• Fig. 9D is a schematic representation, in flow chart form, of yet another electrochemical displacement reaction embodiment of the method of the invention, where a fugitive binder is provided in addition to the salt binder, and the body is removed from the original powder bed and settered for further heat treatment;
• Figs. 10A, 10B and IOC are a schematic representation of a method of the invention using molding techniques, showing a mold filled with powdered material (Fig. 10A) , followed by the adding of a liquid salt solution (Fig. 10B) , followed by the removed, molded part (Fig. IOC) ;
• Fig. 11 is an electron micrograph of a cross-section of a skeleton of steel powder, with copper metal at the necks between powder granules , the copper derived from copper nitrate solution, where the product was dried and fired at 480°C, to reduce but not melt the copper;
• Fig. 12 is an electron micrograph of a cross-section of a copper bound product with a skeleton of molybdenum powder, the copper derived from copper nitrate solution, where the product was dried and fired at 1110°C, to melt the copper;
• Fig. 13 is an electron micrograph of a cross-section of a skeleton of tool steel powder into which a salt of copper sulfate has been printed and undergone a displacement reaction, where the product has been dried, but not fired;
• Fig. 14 is an electron micrograph of a cross-section of a copper bound product with a skeleton of tool steel powder, the copper derived from copper sulfate solution as shown in Fig. 13, where the product has been dried, removed from the original powder bed, settered and fired at 1110°C;
• Fig. 15 is an electron micrograph of a cross-section of a silver bound product with a skeleton of molybdenum powder, after a displacement reaction with silver carbonate salt solution, where the product has been dried but not fired;
• Fig. 16 is an electron micrograph of a cross-section of a silver bound product with a skeleton of molybdenum powder, after a displacement reaction such as shown in Fig. 15, where the product has been dried and fired at 980°C;
• a binder In general, concentrated metal salt solution is used as a binder. After applying such a solution to the powder, the entire powder body is maintained at a temperature, below the sintering temperature of the powder, T ⁇ , in a reducing atmosphere. Under appropriate conditions, a binder that originates from the salt adheres to the powder particles adjacent points where the powder granules contact each other and binds the regions that contain the salt. (It will be understood that the temperature at which a powder will begin to sinter also depends on the duration over which the powder is observed. As used herein, T ⁇ x, is the temperature at which the powder will sinter over a reasonable period of time for manufacturing purposes, on the order of less than one day.)
• FIGs. 1A and IB show, schematically, a comparison between a sintering method (Fig. 1A) and a salt based method (Fig. IB) .
• loose powder particles 202 and 204 are heated to a temperature at which they sinter, along processing path S. Due to migration of material from the particles to the necks, sintering reduces the total surface area of the body of powder, and also generally reduces the distance d between nominal centers C of the individual powder grains, thus causing the entire part to shrink along the axis along which the centers approach. In a three dimensional part, shrinkage is through three dimensions.
• Joining is not accomplished by joining of a portion of the particles themselves. Thus, there is little or no shrinkage.
• Another advantage of the current invention is to make the skeleton less susceptible to shrinkage during thermal treatments.
• the driving force for shrinkage during sintering is the reduction of surface area that accompanies the formation of necks between particles. Creating necks by adding material substantially reduces this driving force. With the invention, it is possible to maintain shrinkage (linear) to below 2%, and even less, even as low as .1%
• 60 micron spherical silver powder was found to shrink 1.1% when fired at a temperature of 650 'C in a furnace cycle with a total duration (heat, hold and cool) of approximately 3 hours under forming gas (5% Hydrogen, 95% Argon) .
• 60 micron spherical silver powder was saturated with 3.5 M solution of AgN0 3 in ammonia, dried, and then fired. When subjected to an identical firing cycle, this sample was found to shrink less than 0.1%. It is believed that silver necks formed by the reduction of the silver nitrate reduced the driving force for sintering, namely the propensity to reduce surface area, resulting in dramatically less shrinkage.
• the invention also has the advantage that the powder material is placed, and then remains stationary while the binder material is placed, or added.
• the powder material is not further mixed, agitated, moved, extruded, forced, etc. There is substantially no relative motion between particles.
• This is advantageous because it is well known and controllable how to place, transport and shape dry powder. It is more difficult and less certain how to handle powder that has been mixed with a liquid, such as a slurry.
• a slurry results in a lower packing fraction, lower density, and more inhomogeneity than using dry powder. Further, it allows total control over the location of placing the binder solution. This permits making a part of virtually any shape, according to the 3D Printing techniques.
• a solution of a liquid carrier that contains a metal salt is printed at selected regions of a layer of a powder bed, analogous to the means by which liquid polymer binders are printed, as described in U.S. Patent No. 5,204,055 Sachs et al., referred to above.
• the printing technique is described in detail in connection with Figs. 2A, 2B, 2C, 2D and 2E, at col. 4 of the 5,204,055 Patent.
• the liquid dries completely, or almost completely away, leaving behind a recrystallized film of salt.
• the salt film itself binds to the powder material, and to other salt particles, forming bridges between the powder particles of a single layer, and between powder particles of adjacent layers, as shown in Fig. 2F.
• a first layer of powder is provided, and a pattern of the binding liquid is printed thereon.
• the pattern is provided in regions where it is desired to join the powder particles to other particles in the same layer, and also to particles in the layer that has been laid before the current layer.
• a next layer of powder is provided, and this next layer is also printed upon, again in regions where it is desired to join the next layer to the previously printed layer, and within the next layer.
• the '055 Patent mentioned above discusses using different binders, including polymeric resins and colloidal silica.
• the present invention uses a novel binder solution that contains a metal salt . This solution acts as a binder in a novel fashion, as discussed below.
• the overall method of this embodiment of the invention is shown schematically with reference to Figs. 2A, 2B, 2C, 2D, 2E and 2F and in flow chart form with reference to Fig. 3.
• the process begins 400 with the step of providing 440 a layer of powder, as described above.
• the powder particles 302 are shown to be spherical, which is a preferred embodiment.
• the size distribution is "monomodal" meaning it has an average size distribution and some spread around it but the spread is controlled. In another preferred embodiment, the size can be uniform. However, it is also possible to use a range of sizes of particles, and further, to use particles that are not spherical.)
• Each layer 308 is typically at least three particles thick, due to issues of powder flowability and layer spreadability .
• Typical deposited layers can also be thicker.
• layer means that amount of powder material that is deposited and then printed upon, before an additional such layer is deposited on top of the first layer.
• the next step is to print 442 a salt solution 306 in the regions of the powder particles 302 that will be bound, as shown in Fig. 2B.
• a salt solution 306 is drawn by capillary action to the regions 310 where adjacent powder particles 302 touch each other.
• the volume of crystallized salt is exaggerated in Fig. 2C for purposes of illustration.
• Figs. 4 and 6 are electron micrographs of actual samples that show the scale of constituents.
• Fig. 4 shows rochelle salt printed on steel powder and dried.
• Fig. 6 shows silver nitrate.
• salt particles 312 are left at the necks 310.
• a query is conducted to determine 446 if the full shape has been built up. If not, the method of the invention returns to the step 440 of providing a layer of powder, as shown in Fig. 2D.
• a new layer 308' is provided on top of the first layer 308.
• a salt solution 306' is again provided 442 to the locations of the layer 308' where it is desired to join grains of powder to each other within the layer, and between layers, as shown in Fig. 2E. It should be noted that as shown in Fig. 2E, the location of the salt solution applied to the layer 308' is essentially identical to the locations where the salt solution was applied to the layer 308. This would not typically be the case for all adjacent layers, and again is shown this way only for simplicity.
• the salt solution 306' also dries 444 to form a recrystallized film of salt.
• the salt solution may include thickening agents such as methyl cellulose or gelling agents such as Alginates or animal gelatin that will cause the solution to become substantially immobilized.
• thickening agents such as methyl cellulose or gelling agents such as Alginates or animal gelatin that will cause the solution to become substantially immobilized.
• drying could take place later, such as after the entire part is formed. In many cases, this will result in time saving for part forming.
• the unbound powder is removed 448, such as by vibration, or other appropriate techniques that are not so vigorous as to disrupt the salt film structure.
• the three dimensional shape is densified 452, typically by being infiltrated 454 with an infiltrant, according to any known infiltration technique and the process ends 458.
• the result is a three-dimensional body that is fully dense, and that has shrunken very little, if at all, from the size and shape into which the solution was printed.
• a suitable infiltrant is an epoxy.
• Epoxy is liquid at temperatures that are low enough so that the salt films will not degrade.
• Many epoxies are liquid at room temperature.
• salts are non-wetting for most metals.
• a metal infiltrant has difficulty infiltrating past the salt regions in the body.
• the epoxy wets the skeleton and can be infiltrated under the action of capillarity from below or by gravity from above.
• Salt candidates for the recrystallization embodiment should impart sufficient strength to the dried body so that it can withstand processing steps, such as infiltration.
• the choice depends on the composition and size of the powder material, the infiltrant, and the size of the body.
• the rochelle salt solution was administered to stainless steel powder and allowed to dry, and produced a strong body.
• Figure 4 is an electron photo micrograph of a cross section of such a body, showing clearly the formation of salt bridges between larger, spherical particles.
• the salt may be dissolved in water at a concentration of up to 67.8 g of anhydrous salt per lOOg water (at 20°C) .
• rochelle salt has a melting point of approximately 70 - 80°C, and, therefore, if an epoxy is to be used as an infiltrant, it must cure at a temperature below 70° C.
• cyanoacrylates may have appropriate properties.
• magnesium sulfate MgSO 4 '7H 2 0 (Epsom salt) .
• Magnesium sulfate is relatively safe and has a melting point above 200°C. It has a high solubility in water. Parts bound with magnesium sulfate showed a strength that is high enough to withstand careful handling. They can be infiltrated with epoxy, as discussed above.
• the recrystallization technique can be applied to any powder material, as long as the powder doesn't dissolve in the salt solution. Any infiltrant must cure at a temperature below the melting points of the salt and the powder.
• a salt solution is provided to a powder bed as described above in connection with the recrystallization embodiment .
• the method steps of a first variant of this reducing embodiment of the invention are shown in flow chart form with reference to Fig. 5A.
• the reducing embodiment of the invention may be identical to the recrystallization embodiment, up to the step 444 where the salt solution has been printed at every layer, and then optionally dried.
• an atmosphere is provided 502 and conditions are provided 504 that will result in reduction of the metal from the salt.
• the atmosphere may be a reducing atmosphere, or, in an appropriate case, an inert atmosphere, as discussed below. For this reason, the reducing atmosphere step 502 is indicated as "optional.”
• a first variant of the reducing embodiment of the invention shown in Fig. 5A, all heat treating processing of the body is conducted in the original powder bed.
• the part is maintained 504 in an appropriate atmosphere, for a duration, and at a temperature, that is sufficient to cause metal of the salt to reduce into metal, preferably forming a film 314 on the particles 302, 302', which film joins the particles together (Fig. 2G) .
• the temperature and duration of heating are maintained below T ⁇ , that which would result in any sintering of the powder particles 302 themselves.
• the steps of the method are identical to those of the recrystallization embodiment.
• the unbound powder is removed 448'.
• An infiltrant may be provided 454', or not, as is desired 450'.
• Fig. 11 is an electron micrograph of copper particles that have reduced from a copper nitrate solution onto steel powder.
• Any such metal can contribute to binding the powder if subsequent heat treatment causes these particles to join the metal powder at the necks .
• the heat treatment may cause the metal of the salt, after having reduced, to sinter together, thereby imparting additional strength, toughness, etc. to the body. It should be noted that it is not the main constitutive powder particles of the body that are sintering, but only the deposited metal particles, that originated in the salt.
• the atmosphere under which reduction step 504 takes place may be an inert atmosphere or it may be a specially designed reducing atmosphere, for instance a forming gas atmosphere of hydrogen and argon.
• Other examples of reducing atmospheres include pure hydrogen, and an inert gas with some carbon monoxide content.
• An advantage of this original powder bed variant of the reducing embodiment is that the elevated temperature step is conducted with the forming part remaining in the original powder bed.
• the powder bed provides an automatic and perfectly shaped support for delicate features of the part. Settering is not required.
• the reduction embodiment (and the displacement embodiment discussed in more detail below) is particularly beneficial for situations in which a porous body is desired, and an infiltrant will not be used.
• the reduction embodiment is beneficial in some circumstances, as compared to the recrystallization embodiment, because the reduced metal film typically is stronger than the precipitated, unreduced salt. Further, many crystallized salts are subject to degradation by moisture, being soluble in water. The reduced metals are not subject to such degradation.
• An example of such products are a porous filter, catalyst support, heat spreader (for a liquid) and flow diffusers.
• a metal salt suitable for use with the original powder bed reduction variant of the invention preferably possesses the following properties:
• the reduced metal does not have a detrimental effect on the overall mechanical properties of the part .
• the reduction must occur at a temperature below T MAX to permit easy part retrieval. Otherwise, the unbound powder begins to sinter. (Other variants of the invention are discussed below when the reduction does not occur at a temperature below T ⁇ of the original powder bed.)
• the reduced metal will have a film-like morphology and be adherent to the powder. Further, it is desirable to have as much of the reduced metal at the necks as possible to provide greater strength.
• the salt must be soluble enough in a suitable liquid carrier to provide sufficient metal content in the binder.
• the salt should preferably reduce to a coherent continuous film that provides adequate properties, such as strength, at a temperature below that powder sintering temperature.
• a temperature below that powder sintering temperature For example, using silver nitrate as the salt, as described below, silver metal film is deposited at temperatures of about 450°C, to form strong necks, which temperature is well below the sintering temperature of many useful metal powders .
• Such salts are advantageous because reduction alone results in adequate strength, without there being any need to resort to sintering or melting the metal from the salt (which typically (for the examples set forth herein) occur at higher temperatures than reduction) .
• the melting point of the infiltrant should preferably be lower than the sintering temperature of the base metal powder. More precisely, the temperature required for the infiltration process should preferably not exceed the melting point of either the base powder or the necks. If a metal is used as the infiltrant, then the melting point of the metal should preferably be lower than either of these temperatures. If an epoxy is used for the infiltration, then the curing temperature should preferably be lower than either of these temperatures .
• a similar phenomena occurs in some instances when an infiltrant is used that would be expected to dissolve the metal of the necks. Again, it is believed that capillary stress draws the body together, despite the fact that the infiltrant may have dissolved the metal of the necks.
• a preferred salt to use is silver nitrate, which results in a silver film that joins the powder particles together.
• Copper is a common infiltrant. Copper and copper alloys can be used to infiltrate a silver bound skeleton, despite the fact that the copper alloy may dissolve the silver. In other cases, the rate of dissolution of the metal neck may be sufficiently slow to allow for infiltration and solidification to take place before the neck has dissolved.
• infiltrants include zinc and zinc alloys, lead/tin and silver brazing alloys. It may also be beneficial to use a flux, to aid in wetting the skeleton with the infiltrant.
• the melting point of the infiltrant should generally be less than the sintering temperature of the powder, as discussed above.
• the metal of the infiltrant should preferably not dissolve the metal from the salt.
• the infiltrant should preferably wet both the powder and the metal of the salt, or a flux should preferably be used to aid wetting.
• the infiltrant should not result in dimensional changes of the infiltrated product. Additional concerns for the designer relate to the finished product. It should be tough enough to withstand the stress of the desired use, such as molding, or filtering, etc.
• the deposited metal strongly bond to the powder particles .
• a strong bond is present.
• Such strength may also arise in situations where films do not form, such as when discrete regions of metal form, particularly at the necks.
• silver nitrate melts at 212°C and remains in a liquid state up to the temperature of 440°C, when, from its melted state, it decomposes. More specifically, at this temperature, oxygen, nitrogen and nitrogen oxides are evolved while silver adheres on the stainless steel powder. It is hypothesized by the present inventors that the fact that the component (molten silver nitrate) prior to the formation of the solid silver is in liquid form, is of great importance in the resulting adhesion between silver and steel.
• Silver carbonate in contrast to silver nitrate, does not melt. At around 220°C, it decomposes to silver oxide (Ag 2 0) and carbon dioxide (C0 2 ) . The resulting silver oxide also does not melt. It decomposes to its two elements. It starts to decompose as soon as it is formed and its decomposition rate increases as the temperature increase. (It is known from the literature that the decomposition of silver oxide starts at 189 ° C and becomes rapid at 250°C-300°C) . It should be noted that neither of the two chemical compounds that precede the formation of silver is in a liquid state at any point .
• An important condition to consider is the minimum temperature at which the metal from the salt will reduce.
• One condition that must be satisfied for the salt to reduce to metal is a lowering in the Gibbs free energy of the system.
• Such a condition can be calculated, taking into account the reactants, products, atmosphere and temperature, with the aid of thermodynamic data.
• Such data can be obtained from tables, such as the JANAF thermochemical tables published by the American Chemical Society and the American Institute of Physics for the National Bureau of Standards.
• thermodynamic calculations can also be performed with the aid of computer programs such as "Thermo-Calc" developed at the Royal Institute of Technology, Sweden. In most cases, an increase in processing temperature will favor a reduction of the salt to metal.
• a minimum temperature required for this reduction For instance, Therma-Calc shows that nickel nitrate reduces to pure nickel when fired at around 850°C in the presence of hydrogen and this has been confirmed by experiment.
• This minimum temperature can be used as a guideline to assess the viability of candidate salts, and to help choose among the variants discussed above and illustrated in Figs. 5A - 5D. It should be kept in mind that achieving reduction at a relatively low temperature will provide the designer with more choices of powders for the body of the material . Further, it will make it possible to use more of the variants of the method of the invention shown in Figs. 5A - 5D.
• thermodynamic calculations do not provide any information about the rate of the reaction. They also do not predict the morphology of the resulting product and therefore cannot predict whether the metal will form as a film, or granules, and whether it will adhere or not to a substrate.
• a 1.75 molar solution of copper nitrate (Cu (N0 3 ) 2 '3H 2 0) is used to provide the copper to bind molybdenum powder, as shown in Fig. 12.
• each liter of powder bed will consist of 0.6 liters of powder and .4 liters of salt solution.
• the salt will first decompose to CuO and then reduce to Cu.
• each mole of salt will require 1 mole of Hydrogen gas to effect a reduction.
• Each liter of powderbed, containing as it does 0.7 moles of salt will require 0.7 moles of Hydrogen gas.
• Some salts reduce under a thermal treatment without requiring the presence of hydrogen. This is advantageous in that no considerations need be given to supplying the required amount of gas or allowing it to transport into the skeleton. However, if there are gaseous byproducts, sufficient time must still be allowed for the transport of those gaseous byproducts out of the skeleton.
• any heating of the powder article, either for causing 504 reduction of the metal from the salt, or its sintering or melting would be conducted in the original powder bed into which the salt solution had been deposited. While such a practice is a very advantageous embodiment of the method of the invention, it is not always the most advantageous embodiment.
• the reduced metal may not form a film-like morphology upon reduction, or, if a film is formed, it may not be strong enough to withstand the necessary subsequent handling.
• the material of the powder into which the salt is printed cannot withstand the temperatures that would be required for subsequent sintering or melting of the metal from the salt.
• it is advantageous to setter the printed part in another powder for instance a ceramic powder that can withstand high temperatures, and to then treat the part to sinter or to melt to reduced metal .
• Settering can be conducted at different stages along the process, depending upon the strength of the body at these various stages. For instance, as shown in Fig. 5B, in some cases, the body may be strong enough to remove from the original bed and setter 506B after the step 444 of drying the salt solution to crystals, before any reduction.
• the body can be settered 506B in a different powder material, followed by steps that are similar to those discussed above: provision 502B of a reducing atmosphere, which is optional; providing 504B temperature for a duration sufficient to reduce the salt in the necks to metal, and, if desired, to sinter or melt the reduced metal, as discussed above.
• the settering powder is removed 508 and densification proceeds as described above, if desired.
• Suitable settering powders include ceramic powders, such as alumina, silicon carbide and zirconia powder and metallic powders such as molybdenum, tungsten or other refractory metals. Typically, fairly large powder sizes in the range of 30 - 200 microns would be used to provide for flowability of the settering powder and to minimize the possibility of any sintering of the settering powder.
• the crystallized salt nor the reduced metal provide enough strength to enable removing the body from the original powder bed.
• the polymeric binder is effective at low temperatures to sufficiently bind the powder material, so that the bound body can be removed 501 from the original powder matrix in which it has been formed, and settered 501 in another material (or not settered, for suitably small articles) .
• the polymeric binder material holds the part together.
• all of the heating steps 504' can be conducted in the settered state, including reducing (either in a special atmosphere 502' or an inert atmosphere), sintering of the metal from the salt, and melting of the metal from the salt.
• reducing either in a special atmosphere 502' or an inert atmosphere
• sintering if the part is strong enough or melting
• the settering powder is removed 548 and subsequent treatment is applied as discussed above, for instance densification 552 by infiltration 554 or sintering 556.
• necks that are a combination of two different metals, for instance by providing two (or more) different salts in the salt solution. In choosing the different salts, it is important that the salts not combine into a species that will precipitate out of the solution.
• silver nitrate and copper nitrate may both be provided in the same solution, and used to form a deposit that includes both metals, without any premature precipitation. If silver and copper salts were dried, and then reduced, and then heated to melt the resulting silver and copper metals, an alloy of copper and silver could be formed for increased strength.
• necks that are a species of material that is anywhere along the transformation pathway from salt to metal. Some such species may provide adequate strength.
• An example of a suitable instance of the reduction embodiment as shown in Fig. 5A uses one molar solution of silver nitrate (AgN0 3 ) dissolved in water as the binder.
• a suitable powder is 60 micron diameter spherical 316 stainless steel powder.
• the silver nitrate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the entire powderbed, including the region bearing the salt is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 450°C, held at 450°C for an hour and then cooled at a rate of 5°C/min.
• the silver nitrate decomposes to silver metal and gaseous byproducts (nitrogen, oxygen, nitrogen oxides) .
• gaseous byproducts nitrogen, oxygen, nitrogen oxides
• the result as shown in Fig. 7, is the formation of silver films that cover parts of the larger spherical particles and of strong silver necks between the particles .
• the volume of silver metal reduced will be approximately 0.69% of the volume of the steel powder.
• the part is removed from the powder.
• the shrinkage of the part from the condition in which the salt is dry to the condition in which the metal bound skeleton is formed is measured as 0 to within the experimental error of 0.1%.
• the part may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• Silver Nitrate can also serve as a binder according the pathway of Fig. 5A using Mo, W, tool steel P-20, and tool steel H-13 powders. Hydrogen is not necessary for this example as the silver nitrate will decompose to silver under inert gas, however, the use of forming gas may be preferred to avoid oxidation of the powder by the by-products of the decomposition.
• a suitable instance of the reduction embodiment as shown in Fig. 5A where the powder bed is fired beyond the reduction temperature of the metal, uses a 1.75 molar solution of copper nitrate (Cu(N0 3 ) 2 '3H 2 0) dissolved in water as the binder.
• a suitable powder is 60 micron diameter spherical molybdenum (Mo) powder.
• the copper nitrate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the entire powderbed, including the region bearing the salt is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 1110°C, held at 1110°C for half an hour and then cooled at a rate of 5°C/min.
• copper nitrate reduces to copper oxide (CuO) at about 180°C and then copper oxide reduces to copper.
• the result, as shown in Fig. 12, is the formation of strong copper necks between the particles.
• the volume of copper metal reduced will be approximately 0.83% of the volume of the Mo powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• FIG. 5A Another example of a suitable instance of the reduction embodiment as shown in Fig. 5A uses a 1.3 molar solution of nickel nitrate (Ni (N0 3 ) 2 '6H 2 0) dissolved in water as the binder.
• a suitable powder is 22 micron tungsten carbide (WC) powder.
• the nickel nitrate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the entire powderbed, including the region bearing the salt is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon. The furnace is ramped up at a rate of 5°C/min to a temperature of 1200°C, held at 1200°C for half an hour and then cooled at a rate of 5°C/min.
• nickel nitrate reduces to nickel oxide (NiO) at about 600°C which reduces to nickel. While the reduction of the nickel nitrate to the nickel oxide can be accomplished in a non-reducing atmosphere, the reduction of the oxide to nickel has to be done in a reducing atmosphere.
• the volume of nickel metal reduced will be approximately 0.57% of the volume of the WC powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• Nickel Nitrate can also serve as a binder according the pathway of Fig. 5A using 40 micron spherical alumina powder. The heat treatment on this case is carried out at 1530°C.
• FIG. 5A Another example of a suitable instance of the reduction embodiment as shown in Fig. 5A uses a 0.3 molar solution of nickel acetate (Ni (CH 3 COO) 2 '4H 2 0) dissolved in water as the binder.
• a suitable powder is 22 micron tungsten carbide (WC) powder.
• the nickel acetate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the entire powderbed, including the region bearing the salt is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 1200°C, held at 1200°C for half an hour and then cooled at a rate of 5°C/min.
• the volume of nickel metal reduced will be approximately 0.13% of the volume of the WC powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• FIG. 5A Another example of a suitable instance of the reduction embodiment as shown in Fig. 5A uses a 0.7 molar solution of nickel acetate (Co (CH 3 COO) 2 "4H 2 0) dissolved in water as the binder.
• a suitable powder is 22 micron tungsten carbide (WC) powder.
• the cobalt acetate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the entire powderbed, including the region bearing the salt is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 1200°C, held at 1200°C for half an hour and then cooled at a rate of 5°C/min.
• the volume of cobalt metal reduced will be approximately 0.27% of the volume of the WC powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C. Another suitable infiltrant is Copper metal. The infiltration is carried out at 1250°C under a gas atmosphere.
• FIG. 5B An example of a suitable instance of the reduction embodiment that uses subsequent settering and reducing, and sintering or melting of the crystallized salt, as shown in Fig. 5B is as follows.
• a 0.3 molar solution of nickel acetate (Ni (CH 3 COO) 2 '4H 2 0) is dissolved in water as the binder.
• a suitable powder is 22 micron tungsten carbide (WC) powder.
• the nickel acetate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the printed part is removed from the powderbed before any reduction. It is settered in alumina powder and it is placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon. The furnace is ramped up at a rate of 5°C/min to a temperature of 1200°C, held at 1200°C for half an hour and then cooled at a rate of 5°C/min.
• the volume of nickel metal reduced will be approximately 0.13% of the volume of the WC powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• An example of a process shown in Fig. 5C, that uses subsequent settering and sintering or melting of the reduced metal is as follows.
• An example of a suitable instance of the reduction embodiment as shown in Fig. 5C uses a 1.3 molar solution of nickel nitrate (Ni (N0 3 ) 2 ' 6H 2 0) dissolved in water as the binder.
• a suitable powder is 60 micron spherical Mo powder.
• the nickel nitrate solution is administered to the powderbed, allowed to infiltrate and then dried.
• the entire powderbed, including the region bearing the salt is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon. The furnace is ramped up at a rate of 5°C/min to a temperature of 975°C, held at 975°C for half an hour and then cooled at a rate of 5°C/min.
• the printed part is strong enough to be removed from the powderbed. If more strength is desirable, a second heat treatment might follow: the printed part is settered in alumina powder and placed in the furnace and fired under forming gas at 1200°C. Again, the heating and cooling rate is 5°C/min. The volume of nickel metal reduced will be approximately 0.57% of the volume of the Mo powder. The part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• a copper nitrate-Polyacrylic acid (PAA) solution is prepared in the following proportions: 93 v.o. % of 1.75 molar water solution of copper nitrate (Cu (N0 3 ) 2 '3H 2 0) and 7 v.o. % of PAA solution.
• the latter solution consists of 35 wt% H 2 0 and of 65 wt % PAA.
• the average molecular weight of the used PAA is approximately 2000.
• a suitable powder is 60 micron diameter spherical molybdenum (Mo) powder.
• This copper nitrate-PAA solution is administered to the powderbed, allowed to infiltrate and then dried.
• the printed part is then removed from the powderbed (PAA provides the necessary strength), and it is settered in alumina powder. It is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 500°C. It is held at 500°C in order to burn out the PAA; it is then ramped up at a rate of 5°/min to a temperature of 1110°C, held at 1110°C for half an hour and then cooled at a rate of 5°C/min.
• copper nitrate reduces to copper oxide (CuO) which reduces to copper.
• CuO copper oxide
• the volume of copper metal reduced will be approximately 0.77% of the volume of the Mo powder.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• PAA can be added to any of the solutions discussed above in connection with the discussion of Fig. 5A (all firing steps conducted in the original powder bed) .
• the same concentration of PAA (as in the case of copper nitrate) , produces parts with high green strength.
• a third major embodiment of the method of the invention is to use a salt containing solution that undergoes a displacement reaction with a metal powder.
• the idea of displacement reaction binding is shown in Figs. 8A, 8B, 8C, 8D, 8E, 8F, 8G, 8H and 81.
• a salt solution is printed into a layer 808 of powder particles 802 of a metal that is capable of undergoing an electrochemical displacement reaction with the metal of the salt.
• the metal of the powder provides electrons to the metal of the salt, as the metal of the powder dissolves into the salt solution.
• the solution 806 collects between the particles due to capillary action.
• a thin metal film 830 (metal from the salt) deposits substantially all over the powder particles 802 in the printed regions directly from the solution (Fig. 8C) . The depositing begins almost immediately upon contact of the solution with the powder. This leads to small bridges between the single powder particles 802, within a layer 808, which bridges eventually result in the particles sticking together.
• the printed layer can be dried, as shown in Fig. 8D, where the solution recedes to the necks, as in the embodiments discussed above and deposits 816 form. Alternatively, this drying step can be conducted after several layers have been spread and printed upon.
• Additional layers 808' are added (Fig 8E) and printed with salt solution 806' (Fig. 8F) .
• Metal again deposits directly from solution as thin films 830' around the particles 802' (Fig. 8G) .
• the particles 802' of the additional layer 808' are joined to each other and to the particles 802 of the previously applied layer 808. It is possible to apply further heat treatment to the body (Fig. 81) , which may cause the further reduction of additional metal 818 from the remaining dried salt 816, thereby adding to the necks .
• Possible candidates for this binder type are solutions and powder combinations where the salt and a portion of the metal powder undergo an electrochemical displacement reaction. As a result of this reaction the metal of the salt (or a portion of it) is deposited on the metal powder.
• This deposition of the metal from ionic solutions consists essentially of adding electrons to the dissolved metal ions (of the salt) . These electrons are provided by the metal powder as it partially dissolves into the solution.
• the bridges formed by this method may consist of metal structures of both the metal of the powder and the metal of the salt in the added salt solution. These structures may include alloys, mixtures, coatings of sequential layers of first one then the other, islands of one in a matrix of the other, or fine particles that are interspersed.
• the upper limit of the amount of the powder reduced can be inferred from the related chemical reaction. For instance, when copper reacts with silver nitrate
• a guideline that may be useful in some circumstances is to compare the relative positions on the electromotive force series of the metal of the powder with the metal of the salt. Generally if the metal of the salt is more noble than that of the powder, then a displacement reaction is more likely to occur. As an example, consider the displacement of copper by iron in the detailed example set forth below.
• Other chemical species present in the solution may make it possible to have a displacement reaction even when the metal of the salt is less noble than the metal of the powder. Such other species include ammonium ions or cyanide ions .
• Fig. 9A shows an embodiment where all of the activity is conducted in the original powder bed.
• the process begins 600, followed by providing 640 a layer of powder.
• the salt solution is printed 642, and directly reduces 644 to metal upon contact. If more shape buildup is required 646, the process returns to the powder laying step 640. If not, the unbound powder is removed 652, and the body is densified, if desired, as discussed above.
• the straight displacement reaction method does not always provide as high a strength or other properties as may be desired. If so, then according to a variant of the method shown in Fig. 9B, the part is heated 650 in the original powder bed to sinter or melt the deposited metal, analogous to the similar step discussed above in connection with the reduction embodiment of the invention in Fig. 5A.
• metal may also reduce from that salt during the heat treatment 650.
• Such unreduced salt may be either or both the salt from the added solution or the salt from the metal powder, formed as described above.
• the product of the displacement reaction as shown in Fig. 9A may be smooth, well defined necks, of the reduced metal (as observed in a scanning electron micrograph, such as Fig. 15, showing silver from silver carbonate deposited on molybdenum powder) .
• these necks may have little strength as deposited, the film may be porous and weak or there may be a weak interface between the film and the powder (as can be seen by small cracks in the necks) .
• elevated temperature heat treatment steps 650 may be used to strengthen the necks, either by sintering or melting the metal of those necks. The result of such steps are shown in Fig.
• any heating 650 of the powder article either for causing sintering or melting of the metal arising from the displacement reaction with the salt, would be conducted in the original powder bed into which the salt solution had been printed. While such a practice is a very advantageous embodiment of the method of the invention, it is not always the most advantageous embodiment.
• the reduced metal may not form a film-like morphology upon reduction, or, if a film is formed, it is not strong enough to withstand the necessary subsequent handling.
• the material of the powder into which the salt is printed cannot withstand the temperatures that would be required for subsequent sintering or melting of the metal from the salt.
• the part is relatively small (less than two inches (5 cm) in maximum dimension) it may not need to be settered.
• Fig. 9C One method of dealing with this situation is shown in Fig. 9C. If the reduced metal provides enough strength to permit handling the body, after the salt is reduced 644 to metal and optionally dried, the body is removed 652C from the original powder bed and settered in another, higher melting temperature powder bed.
• Fig. 13 is an electron micrograph which shows copper reduced onto tool steel from a copper sulfate solution, which provides enough strength to remove and setter the part. Crystallized, unreduced salt may also contribute to the strength of the body, as discussed above in connection with the crystallization embodiment shown in Fig. 3.
• Fig. 14 shows a copper bound steel part, as shown in Fig. 13, after settering and firing at 1110°C to melt the copper metal. The settering powder is removed 648, and the body is densified, if desired.
• the reduced metal does not provide enough strength to permit removing the body from the original powder.
• a polymer can be added to the salt solution that is to be printed, and the two can be printed together 642 ' .
• the metal reduces directly from the salt solution to the powder.
• the polymer acts as a binder, enabling the part to be removed 647 and settered in another, higher temperature powder.
• the body is then heated 650' to remove the polymer binder, and sinter or melt the reduced metal, as described in connection with the above embodiments.
• the settering powder is removed 652', and the body is infiltrated, or not, as desired.
• a further advantage of the displacement reaction method of the invention is that the reduction of the metal takes place in solution, without the need for a reducing gas, such as hydrogen, discussed above.
• FIG. 9B An example of a suitable instance of the displacement embodiment as shown in Fig. 9B, where after reduction, the body is fired, uses a 0.3 molar solution of silver carbonate (Ag 2 C0 3 ) .
• the solvent consists of the following: 87 v.o. % H 2 0 and 13 v.o. % ammonium hydroxide (ACS, 29.6% NH 3 ) .
• a suitable powder is 60 micron diameter spherical molybdenum (Mo) powder.
• the silver carbonate solution is administered to the powderbed. Silver is deposited on the powder by means of displacement reaction as shown in Fig. 15.
• the entire powderbed is then placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 980°C, held at 980°C for half an hour and then cooled at a rate of 5°C/min.
• the result is the formation of silver films that cover parts of the large particles. Some of these films bind the Mo particles as seen in Fig. 16.
• the volume of silver metal will be approximately 0.41% of the volume of the Mo powder. The part is removed from the powder.
• the shrinkage of the part from the condition in which the salt is dry to the condition in which the metal bound skeleton is formed is measured as 0 to within the experimental error of 0.1%.
• the part may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• FIG. 9C An example of a suitable instance of the displacement embodiment as shown in Fig. 9C, where the part is removed from the original powder bed and settered and fired uses a 0.6 molar solution of copper sulfate (CuS0 4 ) dissolved in water as the binder.
• a suitable powder is 60 micron diameter spherical tool steel P-20 powder.
• the copper sulfate solution is administered to the powderbed. Copper is deposited on the powder by means of displacement reaction.
• the printed part has enough strength to be removed from the powderbed.
• the printed part is then settered in alumina powder and placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 1110°C, held at 1110°C for half an hour and then cooled at a rate of 5°C/min.
• the volume of copper metal reduced will be approximately 0.28% of the volume of the steel powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• the average molecular weight of the used PAA is approximately 2000.
• a suitable powder is 60 micron diameter spherical molybdenum (Mo) powder. The solution is administered to the powderbed.
• Silver is deposited on the powder by means of displacement reaction.
• the PAA binds the silver-coated Mo powder.
• the printed part is removed from the Mo powder. It is then settered in alumina powder and then it is placed in a furnace under an atmosphere of forming gas consisting of 5% hydrogen and 95% argon.
• the furnace is ramped up at a rate of 5°C/min to a temperature of 500°C. It is held at 500°C in order to burn out the PAA; it is then ramped up at a rate of 5°/min to a temperature of 980°C, held at 980°C for half an hour and then cooled at a rate of 5°C/min.
• the volume of silver metal reduced will be approximately 0.38% of the volume of the Mo powder.
• the part is removed from the powder and may then be infiltrated if a fully dense part is desired.
• a suitable infiltrant is Epoxy PR-500, an aerospace epoxy from 3M. The infiltration is carried out in an oven at a temperature of 175°C.
• the designer should determine the solubility limit, and then use different concentrations below the limit to determine a high enough concentration to provide the desired strength. A balance is then struck between having enough salt to provide the desired strength but not so much to as to cause precipitation of the salt.
• a salt solution When a salt solution is printed into the powder bed, it arrives at an equilibrium configuration, where the salt solution may not completely fill the voids in the powder bed. That is, immediately upon printing it may completely or nearly completely fill the voids, but capillarity then draws some of the liquid off into surrounding powder until an equilibrium configuration is reached. In spherical powder, this equilibrium configuration may typically result in about 60% of the void volume being filled by liquid. At this stage, the liquid in the voids is connected. As it dries, it becomes disconnected. At a stage near the end of drying, there is just a small bit of liquid at each particle neck and as the particle necks are not connected, neither will the liquid be. As the liquid evaporates, the remaining liquid tends to collect at the necks between the particles. This action tends to draw the salt into the necks which is exactly where it is desired.
• the salt solution is printed at full saturation, as the drying takes place, some salt will immediately precipitate that will not have had a chance to migrate to the necks. However, as it takes a while for salt to come out of the supersaturated solution, most of the salt will likely be drawn to the necks, as desired.
• Metal salt solutions can be used as binders for various 3D Printing system configurations.
• the binder can be printed using a drop-on-demand ("DOD") printer. With this device, a drop of printing fluid is not produced at the nozzle, unless it is desired to print the drop on the target.
• the drop is typically produced using a piezo-electric crystal, as is well known.
• An example of a suitable piezo type ink-jet printhead is a nine-nozzle system "ink-jet printing mechanism, model PT 88S" provided by Siemens, Inc.
• Some metal salts are highly corrosive of components that are normally found in printheads .
• the corrosive properties of potential salt binder candidates must be considered.
• silver nitrate could be printed into beryllium powder using a drop on demand type printer.
• Molded Bodies
• a mold 1000 is provided, having the desired shape.
• the mold is filled with powder 1002 according to any appropriate method.
• a salt solution 1006 is added to the entire body of powder.
• the salt solution is allowed to dry.
• the process ends with the formation of crystalline salt of a sufficient strength to hold the body 1060 together such that it can be removed from the mold, as shown in Fig. IOC.
• the dried body is further processed under atmosphere and heat conditions that give rise to reduction of elemental metal, as discussed above.
• the metal joins adjacent powder grains together, and the entire body has significant strength.
• the powder is first placed in the mold, and distributed throughout the mold, as desired. Then, the liquid binder solution is added. This two step procedure has advantages in some situations, as it allows handling of the powder in a dry state. Dry handling of powder is frequently easier to accomplish or more regular than wet powder handling. However, rather than charging the mold with the powder and then applying the salt solution, it is also possible to mix the salt solution with the powder before providing the powder to the mold.
• the desired end product is a porous body with interconnected porosities and an interconnected skeleton.
• a product is useful as a filter, or catalyst body or flow diffuser.
• a fully dense body is desired. According to either the recrystallization or the reduction embodiment, an infiltrant can be subsequently provided to density the body.
• the displacement reaction method can also be used with a molding technique.
• the mold is charged with powder, and then the liquid salt binder solution is provided throughout the mold. Essentially simultaneously with the introduction of the salt solution, metal starts to deposit onto the surface of the metal powder. This displacement reaction proceeds according to its natural course as discussed above.
• the powder 1002 may be applied totally dry, so that it flows well and packs well.
• the salt solution 1006 is then applied and is allowed to infiltrate by capillarity. Next, it is dried. Care must be taken in controlling the drying process, because as the solution dries it tends to be drawn to the outside of the part, that is, toward the surface from which the drying is taking place. If uncontrolled this could result in an inadequate amount of salt in the interior of the body. To some extent, this may be controlled by drying slowly. However, another approach is to add a gelling agent to the salt solution, which will cause the liquid to be bound locally.
• a third possibility is to make the salt solution composed of two distinct liquid phases, one of which evaporates before the other. After the evaporation of the first liquid phase, the remaining liquid is distributed in discrete and unconnected necks at the powder particles and therefore results in local recrystallization of the salt.
• use of the method of the invention with a molding technique may be limited to some extent by the fact that the liquid, and thus the dissolved salt, tends to accumulate more densely at the surfaces of regions of powder where drying takes place.
• a layered technique such as 3D Printing discussed above, non-uniformities through the thickness of a layer can be minimized by reducing the layer thickness until the non-uniformities are acceptable.
• a similar resolution of the problem may be conducted with molding techniques, by providing powder material to the mold in layers of a thickness determined to minimize the migration of salt during drying. In such a case, it is particularly beneficial to apply the powder in a dry state.
• the mold will not be able to withstand necessary heat treating steps, either to reduce, sinter or melt the metal that is derived from the salt . In such cases, it is possible to remove the forming part from the mold and replace it with a refractory material, such as a settering powder.
• Some salts may be printed in the molten state.
• the advantage of this approach, over dissolving salts and printing the solution, is that a larger volume of salts may be printed. Further, some salts may not be readily soluble in an acceptable solvent .
• the salt can be applied in manners other than as a liquid solution or a molten salt.
• the salt in three dimensional printing, can be applied by first spreading a layer of metal or ceramic powder and then selectively applying the salt as a further material in the condition of a slurry of salt in a liquid vehicle (a liquid in which the salt does not dissolve or which is already saturated with the salt) .
• the salt can be applied as a dry powder not in a liquid vehicle, for example by techniques of dusting powder through a stencil mask.
• the part can be further processed for example, by firing the part in the powder bed to reduce the salt to metal and, if needed to sinter or melt the metal of the salt to increase strength.
• Other processing paths described in detail above, such as removing the part when it is lightly bound by either salt crystals, reduced metal, or a polymer, or a combination thereof, can also be applied.
• the salt may be provided in the entire layer of powder as spread with no specification of position in the layer. This can be accomplished by spreading a layer of metal or ceramic powder which is mixed with a fine powder of salt or by coating the metal or ceramic powder with a layer of salt.
• a coating can be created, for example by milling the powder in a solution of salt, drying the powder and then dry milling to break the powder into individual particles. Other powder coating techniques known in the art can be used.
• a polymeric binder can then be applied as a further material to define the geometry of the part in the layer. For example, a solution of polyacrylic acid in water can be ink-jet printed into the layer of powder. This solution can dissolve the salt and provide green strength.
• the part can then be removed from the powderbed and processed according the several methods described above. In some cases, no polymeric additive will be needed in the printed liquid as the dissolved salt may provide sufficient strength for part removal, as discussed above. It should be noted that this mode may be practiced with re-crystallization of salt, thermal reduction of salt or displacement reaction reduction of salt. Further, in this mode, it will be preferred to remove the part from the powderbed before further processing as it will be difficult to distinguish between the regions where liquid was or was not printed.
• dry salt for example by creating a mix of dry salt with metal or ceramic powder, or by coating the powder with salt.
• printing salt or solutions of salt may be an effective way to provide a metallic binding element.
• the conventional practice is to mix fine tungsten carbide powder with fine cobalt powder.
• one micron tungsten carbide powder and one micron cobalt powder can be mixed in the appropriate volume fractions and a slurry can be used to create spray dried powder. This spray dried powder is then caused to flow into a pressing die. A green cutting insert is then pressed. The insert is then liquid phase sintered to produce a fully dense part.
• the cobalt may be provided through a solution of a cobalt salt such as cobalt acetate.
• a cobalt salt such as cobalt acetate
• a layer of fine tungsten carbide powder may be deposited and a solution of cobalt acetate may be printed into this powder to both define the geometry of the part and to provide the source for cobalt.
• tungsten carbide powder is fine, it may be beneficial to deposit the tungsten carbide powder by jetting it in a slurry, as described in a patent application filed under the Patent Cooperation Treaty, designating the US for national phase treatment, under serial number PCT/US98/12280, entitled JETTING LAYERS OF POWDER AND THE FORMATION OF FINE POWDER BEDS THEREBY, in the names of Sachs et al, the disclosure of which is hereby incorporated by reference herein.
• One advantage of this embodiment of the invention is that there is no need to mix powders. When powders are mixed, they sometimes have a tendency to separate (unmix) .
• Another advantage is that more or less of the added material can be placed in different positions. In the known techniques, a relatively homogeneous mix is obtained.
• the powder particles may be any shape. Beneficial results have been achieved using gas atomized spherical metal particles. This results in very regular shapes, which flow nicely and are not too difficult to handle. Further, spherical particles provide close to the highest possible packing density, thereby requiring the minimum infiltration. On the other hand, irregular shaped powder particles can also be used. Typically, the particles are on the order of 10 to 200 microns. Such powders, when used in the layered processes described above, may be spread into a new layer as dry powder. Finer powders, such as in the range of 0.5 - 10 microns may be used as well. However, these will typically have to be applied as a slurry and dried (for example as per the method of patent application serial number PCT/US98/12280 identified above, prior to the administration of a salt solution.
• a wide range of types of powder may be used for the body of the part being formed, including both metals and ceramics.
• the powder must have a sufficiently high enough sintering temperature, T, ⁇ , relative to the temperature at which the salt reduces (or, in the case of the crystallization embodiment, crystallizes) , so that the powder will not begin to sinter.
• the powder should be a substance to which the metal of the chosen salt will adhere. In the case of the displacement reaction embodiment, the powder must be a metal .
• Suitable metals include nickel, copper, bronzes, brasses, titanium, titanium alloys, and refractory metals such as tantalum, molybdenum, and tungsten.
• Suitable ceramic materials include tungsten carbide, titanium carbide and alumina. Some ceramics will be better wetted by metals than others . Silver Nitrate salt solution printed on any of these types of powder provides acceptable results.
• metal powder shall mean any powder having a metal surface, whether that surface is a coating, for instance around a ceramic powder granule, or a part of a wholly metal particle.
• the powde can oe pre- ccated with salt or mixed with fine dry salt, as discussed above.
• the laser sintering can then cause m-situ thermal reduction of the salt to metal, to create a metal containing part as discussed above.
• a polymeric binder can be included m the powder as well and the laser sintering can define a green part by polymer binding.
• the salt can be supplied with a metal or ceramic powder m the extrusion feedstock.
• the salt can be dissolved in the binder material (typically a thermoplastic or other polymer) of the feedstock, included as particles in the feedstock binder, or coated on the metal or ceramic particles .
• the prepared sheet can include salt dissolved m the binder material (typically a thermoplastic or other polymer) of the feedstock, or the salt can be included as particles m the feedstock binder, or coated on the metal or ceramic particles.
• the binder material typically a thermoplastic or other polymer

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• 1998
  • 1998-09-25 JP JP2000512650A patent/JP4314396B2/ja not_active Expired - Lifetime
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